EP2527594B1 - Zufälliges Propylencopolymer mit hoher Steifigkeit und geringer Trübung - Google Patents

Zufälliges Propylencopolymer mit hoher Steifigkeit und geringer Trübung Download PDF

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EP2527594B1
EP2527594B1 EP11189574.4A EP11189574A EP2527594B1 EP 2527594 B1 EP2527594 B1 EP 2527594B1 EP 11189574 A EP11189574 A EP 11189574A EP 2527594 B1 EP2527594 B1 EP 2527594B1
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Prior art keywords
propylene copolymer
equal
fraction
range
iso
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French (fr)
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EP2527594A1 (de
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Petar Doshev
Pauli Leskinen
Markus Gahleitner
Elisabeth Potter
Saeid Kheirandish
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Borealis AG
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Borealis AG
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Priority to ES11189574.4T priority Critical patent/ES2462165T3/es
Priority to PL11189574T priority patent/PL2527594T3/pl
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins

Definitions

  • the present invention relates to a new propylene copolymer and applications made therefrom.
  • the haze should be acceptable. Particularly, a good balance between stiffness and haze is desirable.
  • a high degree of crystallinity of polypropylene renders the material rather stiff, however also increases the haze.
  • the crystallinity is influenced by the amount of comonomer contained in the polymer and by the molecular weight of the polymer chains, i.e. by the molecular weight distribution.
  • a higher amount of comonomer means more interruption of the isotactic polypropylene units and hence less crystallinity. To a certain extent this entails improved optical properties, i.e. better haze values.
  • the stiffness is reduced thereby. Hence, the balance of stiffness and haze is of great importance.
  • EP 1 873 173 provides a polypropylene copolymer with a rather high melt flow rate value, namely an MFR 2 of 70 g/10 min or more. This means a rather low molecular weight which is achieved by the known method of visbreaking. During visbreaking the polypropylene chains received from the polymerization reactor are subjected to degradation by applying peroxide compounds. The result is that the polymer chains are cut statistically and a material with a higher MFR 2 -value is received.
  • EP 2 281 851 provides polypropylene compositions with melt flow rates up to 60 g/10min.
  • the compositions with such high melt flow rates MFR 2 suffer already from extreme high haze values and low impact values. Further the polymerization process for obtaining such compositions could be further improved in view of productivity.
  • the propylene copolymer (R-PP) comprises a propylene copolymer fraction (C-A) and a propylene copolymer fraction (B) in the weight ratio [(C-A)/(B)] of 30/70 to 70/30, wherein said propylene copolymer (R-PP) has
  • the finding of the present invention is to provide a sequential polymerization process wherein at least in the first reactor the temperature is rather high, i.e. equal or more than 70 °C, and the polymerization is run in the presence of a solid catalyst system with very low porosity, i.e. with a pore volume measured according to ASTM 4641 of less than 1.0 ml/g, obtaining thereby the above propylene copolymer.
  • a process for the preparation of a propylene copolymer (R-PP) comprising a polypropylene fraction (A) and a propylene copolymer fraction (B) is a sequential polymerization process comprising at least two reactors connected in series, wherein said process comprises the steps of
  • the instant propylene copolymer (R-PP) is produced in a sequential polymerization process.
  • the term "sequential polymerization process" indicates that the propylene copolymer (R-PP) is produced in at least two reactors connected in series.
  • step (A) i.e. in the first reactor (R-1), preferably in the slurry reactor (SR), like in the loop reactor (LR), the temperature is more than 65 °C, preferably equal or more than 70 °C, yet more preferably equal or more than 75 °C, still more preferably in the range of equal or more than 65 °C to equal or below 95 °C, still more preferably in the range of equal or more than 70 °C to equal or below 90 °C.
  • the pressure in step (A), i.e. in the first reactor (R-1), preferably in the slurry reactor (SR), like in the loop reactor (LR), is within the range of 25 bar to 80 bar, preferably between 30 bar to 70 bar. Hydrogen can be added for controlling the molar mass in a manner known per se.
  • step (A) is transferred to the second reactor (R-2), i.e. to the gas phase reactor (GPR-1), i.e. to step (D), whereby the temperature in step (D) is preferably within the range of equal or more than 75 °C to 100 °C, more preferably within the range of equal or more than 80 °C to 95 °C.
  • step (D) i.e. within the second reactor (R-2), preferably within the gas phase reactor (GPR-1), the pressure is within the range of 5 bar to 50 bar, preferably between 15 bar to 40 bar. Hydrogen can be added for controlling the molar mass in a manner known per se.
  • the residence time can vary in both reactor zones.
  • the residence time in bulk reactor is in the range 0.2 to 4 hours, e.g. 0.3 to 1.5 hours and the residence time in gas phase reactor (GPR) will generally be 0.2 to 6.0 hours, like 0.5 to 4.0 hours.
  • GPR gas phase reactor
  • pre-polymerization (P) prior to the polymerization in the first reactor (R-1).
  • the pre-polymerization (P) can be conducted in the first reactor (R-1), however it is preferred that the pre-polymerization (P) takes place in a separate reactor, so called pre-polymerization reactor (P-R).
  • a pre-polymerization reactor is of smaller size compared to the first (R-1) and second (R-2) reactor, respectively.
  • the reaction volume of the pre-polymerization reactor (P-R) will be between 5 % and 30 % of the reaction volume of the first reactor (R-1), like the loop reactor.
  • the pre-polymerization (P) is performed in bulk or slurry as defined for the first reactor (R-1) above.
  • the pre-polymerization temperature is rather low, i.e. equal or below 50 °C, more preferably between equal or more than 10 °C to equal or below 50 °C, yet more preferably between 12 to 45 °C, even more preferably between 15 to 40 °C, like between 18 and 35°C.
  • the pressure during pre-polymerization can be between 20 to 80 bar, preferably between 25 to 75 bar, like 30 to 70 bar. Residence times can vary between 0.1 to 1.5 hours, like between 0.2 and 1.0 hours.
  • a polypropylene (Pre-PP) is produced which differs from the propylene copolymer (R-PP) obtained by the instant process.
  • the polypropylene (Pre-PP) obtained in the pre-polymerization step (P) can be a propylene homopolymer (Pre-H-PP) or a propylene copolymer (Pre-R-PP), the latter being preferred.
  • the propylene copolymer (Pre-R-PP) obtained in the pre-polymerization step (P) comprises units derivable from
  • the comonomer content i.e. the ethylene and /or a C 4 to C 12 ⁇ -olefin content, preferably the ethylene content, within the propylene copolymer (Pre-R-PP) is equal or more than 0.5 to equal or below 8.0 wt.-%, more preferably of equal or more than 1.5 to equal or below 5.0 wt.-%.
  • the weight average molecular weight (M w ) of the polypropylene (Pre-PP) produced in the pre-polymerization step (P), i.e. of the propylene homopolymer (Pre-H-PP) or the propylene copolymer (Pre-R-PP), is rather low.
  • the polypropylene (Pre-PP), i.e. the propylene homopolymer (Pre-H-PP) or the propylene copolymer (Pre-R-PP) has weight average molecular weight (M w ) of below or equal 300,000 g/mol, more preferably below 100,000 g/mol.
  • the weight average molecular weight (M w ) is in the range of 3,000 to 300,000 g/mol, more preferably in the range of 5,000 to 100,000 g/mol.
  • the weight ratio of the polypropylene (Pre-PP), i.e. of the propylene homopolymer (Pre-H-PP) or the propylene copolymer (Pre-R-PP), and the solid catalyst system (SCS) is below 1000, more preferably below 700, yet more preferably below 500, still yet more preferably below 450. It is especially preferred that the weight ratio of the polypropylene (Pre-PP), i.e. ofthe propylene homopolymer (Pre-H-PP) or the propylene copolymer (Pre-R-PP), and the solid catalyst system (SCS) is in the range of 20 to 1000, more preferably 50 to 700, yet more preferably 70 to 500, still more preferably 80 to 450.
  • the solid catalyst system (SCS) as defined in more detail below is preferably dispersed into polypropylene (Pre-PP), i.e. into the propylene homopolymer (Pre-H-PP) or the propylene copolymer (Pre-R-PP). Thereby the solid catalyst system (SCS) is distributed within the polypropylene (Pre-PP).
  • the term "distributed” shall preferably indicate that the solid catalyst system (CSC) is not concentrated at one place within the polypropylene (Pre-PP) but (evenly) dispersed within polypropylene (Pre-PP). This has the advantage that - contrary to commercially available supported catalyst systems -an overheating at the beginning of the polymerization process due to "hot spots" areas caused by concentration of catalytic species at one place is diminished.
  • one further important aspect of the present invention is that a specific catalyst system must be used in the instant polymerization process.
  • the solid catalyst system (SCS) used comprises
  • the metal is preferably brought in the solid catalyst system (SCS) as a metal compound (CM) which forms with the internal electron donor (ID) or its precursor (P-ID) a complex (C).
  • CM metal compound
  • P-ID precursor
  • C complex
  • the transition metal is preferably brought in the solid catalyst system (SCS) as a transition metal compound (CT). Further information concerning this matter is provided below.
  • a remarkable feature of the used catalyst system (SCS) is that it is of solid form.
  • the aggregate state (solid state) of the catalyst system (SCS) differs from the aggregate state of the reactants, i.e. the propylene and optionally other ⁇ -olefins used.
  • the catalyst system (SCS) used in the present invention is a so-called self-supported catalyst system, or in other words the solid catalyst system (SCS) used does not comprise in significant amounts catalytically inert material used normally as support material.
  • Inert support material is any material which is used to decrease solubility of the catalyst systems in media which are generally used in polymerization processes as well in common solvents like pentane, heptane and toluene.
  • Typical inert support materials are organic and inorganic support materials, like silica, MgCl 2 or porous polymeric material. These support materials are generally used in amounts of at least 50 wt.-%, more preferably of at least 70 wt.-%.
  • the amount of such an inert support material within the solid catalyst system (SCS) is of not more than 10.0 wt.-%, yet more preferably below 5.0 wt.-%, yet more preferably not detectable.
  • the solid catalyst system has a surface area measured according to the commonly known BET method with N 2 gas as analysis adsorptive (ASTM D 3663) of less than 30 m 2 /g, e.g. less than 20 m 2 /g. In some embodiments the surface area is more preferably of less than 15 m 2 /g, yet more preferably of less than 10 m 2 /g. In some other embodiments, the solid catalyst system shows a surface area of 5 m 2 /g or less, which is the lowest detection limit with the methods used in the present invention.
  • the solid catalyst particle (SCS) can be additionally or alternatively defined by the pore volume measured according to ASTM 4641.
  • the solid catalyst particle (SCS) has a pore volume of less than 1.0 ml/g.
  • the pore volume is more preferably of less than 0.5 ml/g, still more preferably of less than 0.3 ml/g and even less than 0.2 ml/g.
  • the pore volume is not detectable when determined according to ASTM 4641.
  • the solid catalyst particle typically has a mean particle size of not more than 500 ⁇ m, i.e. preferably in the range of 2 to 500 ⁇ m, more preferably 5 to 200 ⁇ m. It is in particular preferred that the mean particle size is below 80 ⁇ m, still more preferably below 70 ⁇ m. A preferred range for the mean particle size is 5 to 80 ⁇ m, more preferred 10 to 60 ⁇ m.
  • the solid catalyst system (SCS) is preferably obtainable, i.e. obtained, by a process comprising contacting
  • one important aspect of the preparation of the solid catalyst system is that neither the complex (C) nor the transition metal compound (CT) are present in solid form during the solid catalyst system (SCS) preparation, as it is the case for supported catalyst systems.
  • the solution of a complex (C) of the metal which is selected from one of the groups 1 to 3 of the periodic table (IUPAC) and the internal electron donor (ID) is obtained by reacting a compound (CM) of said metal with said internal electron donor (ID) or a precursor (P-ID) thereof in an organic solvent.
  • the metal compound (CM) used for the preparation of the complex (C) may be any metal compound (CM) which is selected from one of the groups 1 to 3 of the periodic table (IUPAC). However it is preferred that the complex (C) is a Group 2 metal complex, even more preferred a magnesium complex. Accordingly it is appreciated that the metal compound (CM) used in the preparation of said complex (C) is a Group 2 metal compound, like a magnesium compound.
  • CM metal compound
  • IUPAC periodic table
  • the metal compound (CM) to be produced is selected from the group consisting of a Group 2 metal dialkoxide, like magnesium dialkoxide, a complex containing a Group 2 metal dihalide, like magnesium dihalide, and an alcohol, and a complex containing a Group 2 metal dihalide, like magnesium dihalide, and a Group 2 metal dialkoxide, like magnesium dialkoxide.
  • the metal compound (CM) which is selected from one of the groups 1 to 3 of the periodic table (IUPAC), preferably from the Group 2 metal compound, like from the magnesium compound, is usually titaniumless.
  • the magnesium compound is provided by reacting an alkyl magnesium compound and/or a magnesium dihalide with an alcohol.
  • at least one magnesium compound precursor selected from the group consisting of a dialkyl magnesium R 2 Mg, an alkyl magnesium alkoxide RMgOR, wherein each R is an identical or a different C 1 to C 20 alkyl, and a magnesium dihalide MgX 2 , wherein X is a halogen
  • at least one alcohol selected from the group consisting of monohydric alcohols R'OH and polyhydric alcohols R'(OH) m , wherein R' is a C 1 to 20 hydrocarbyl group and m is an integer selected from 2, 3, 4, 5 and 6, to give said magnesium compound (CM).
  • R' is the same or different in the formulas R'OH and R'(OH) m .
  • the R ofthe dialkyl magnesium is preferably an identical or different C 4 to C 12 alkyl.
  • Typical magnesium alkyls are ethylbutyl magnesium, dibutyl magnesium, dipropyl magnesium, propylbutyl magnesium, dipentyl magnesium, butylpentyl magnesium, butyloctyl magnesium and dioctyl magnesium.
  • Typical alkyl-alkoxy magnesium compounds are ethyl magnesium butoxide, magnesium dibutoxide, butyl magnesium pentoxide, magnesium dipentoxide, octyl magnesium butoxide and octyl magnesium octoxide.
  • one R is a butyl group and the other R of R 2 Mg is an octyl group, i.e. the dialkyl magnesium compound is butyl octyl magnesium.
  • the alcohol used in the reaction with the magnesium compound precursor as stated in the previous paragraph is a monohydric alcohol, typically C 1 to C 20 monohydric alcohols, a polyhydric (by definition including dihydric and higher alcohols) alcohol or a mixture of at least one monohydric alcohol and at least one polyhydric alcohol.
  • Magnesium enriched complexes can be obtained by replacing a part of the monohydric alcohol with the polyhydric alcohol. In one embodiment it is preferred to use one monohydric alcohol only.
  • Preferable monohydric alcohols are those of formula R'OH in which R' is a C 2 to C 16 alkyl group, most preferably a C 4 to C 12 alkyl group, like 2-ethyl-1-hexanol.
  • Typical polyhydric alcohols are ethylene glycol, propene glycol, trimethylene glycol, 1, 2-butylene glycol, 1, 3-butylene glycol, 1, 4-butylene glycol, 2, 3-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, pinacol, diethylene glycol, triethylene glycol, glycerol, trimethylol propane and pentaerythritol.
  • the polyhydric alcohol is selected from the group consisting of ethylene glycol, 2-butyl-2-ethyl-1, 3-propanediol and glycerol.
  • the reaction conditions used to obtain the metal compound (CM) which is selected from one of the groups 1 to 3 of the periodic table (IUPAC), preferably the metal compound (CM) of Group 2, even more preferred the magnesium compound, may vary according to the used reactants and agents.
  • said magnesium compound precursor is reacted with said at least one alcohol at temperature of 30 to 80 °C for 10 to 90 min, preferably about 30 min.
  • CM metal compound which is selected from one of the groups 1 to 3 of the periodic table (IUPAC), preferably the metal compound of Group 2, even more preferred the magnesium compound
  • said compound (CM) is further reacted with an internal electron donor (ID) or electron donor precursor (P-ID).
  • ID is preferably a mono- or diester of a carboxylic acid or diacid, the latter being able to form a chelate-like structured complex, preferably a mono- or diester of an aromatic carboxylic acid or diacid.
  • Said carboxylic acid ester or diester preferably the mono- or diester of the aromatic carboxylic acid or diacid, can be formed in situ by reaction of an carboxylic acid halide or diacid halide, i.e. a preferred internal electron donor precursor (P-ID), with a C 2 -C 16 alkanol and/or diol.
  • P-ID preferred internal electron donor precursor
  • CM metal compound
  • P-ID reacts with an internal electron donor precursor (P-ID), i.e. with a dicarboxylic acid dihalide having preferably the formula (I) wherein
  • non-aromatic dicarboxylic acid dihalides the group consisting of maleic acid dihalide, fumaric acid dihalide and their R" substituted derivatives such as citraconic acid dihalide and mesaconic acid dihalide, respectively, are the most important.
  • cyclic, preferably aromatic, dicarboxylic acid dihalides the group consisting of phthalic acid dihalide (1,2-benzene dicarboxylic acid dihalide), its hydrogenate 1, 2-cyclohexane dicarboxylic acid dihalide, and their derivatives, is the most important.
  • said dicarboxylic acid dihalide is phthaloyl dichloride.
  • the magnesium compound is reacted with the dicarboxylic acid halide in a molar ratio Mg total added /dicarboxylic acid halide of 1 : 1 and 1 : 0.1, preferably between 1 : 0. 6 and 1 : 0. 25.
  • the metal compound (CM) which is selected from one of the groups 1 to 3 of the periodic table (IUPAC), more preferably the metal compound of Group 2, even more preferably the magnesium compound, is reacted with the internal electron donor (ID) or with the internal electron donor precursor (P-ID), i.e. the dicarboxylic acid dihalide, under at least one of the following conditions:
  • the organic solvent used for the preparation of the complex (C) can be any organic solvent as long as it is ensured that the complex (C) is dissolved at ambient temperatures, i.e. at temperatures up to 80 °C (20 to 80 °C). Accordingly it is appreciated that the organic solvent comprises, preferably consists of, C 5 to C 10 hydrocarbon, more preferably of a C 6 to C 10 aromatic hydrocarbon, like toluene.
  • Suitable transition metal compounds are in particular transition metal compounds (CT) of transition metals of groups 4 to 6, in particular of group 4 or 5, of the periodic table (IUPAC).
  • CT transition metal compounds
  • Suitable examples include Ti and V, in particular preferred is a compound of Ti, like TiCl 4 .
  • the solid catalyst system can comprise e.g. reducing agents, like compounds of group 13, preferably Al-compounds containing alkyl and/or alkoxy residues, and optionally halogen residues. These compounds can be added into the solid catalyst system (SCS) preparation at any step before the final recovery.
  • the solid catalyst system (SCS) used in the invention may comprise in addition to the catalyst components conventional cocatalyst, e.g. those based on compounds of group 13 of the periodic table (IUPAC), e.g. organo aluminum, such as aluminum compounds, like aluminum alkyl, aluminum halide or aluminum alkyl halide compounds (e.g. triethylaluminum) compounds, can be mentioned.
  • IUPAC periodic table
  • organo aluminum such as aluminum compounds, like aluminum alkyl, aluminum halide or aluminum alkyl halide compounds (e.g. triethylaluminum) compounds
  • one or more external donors can be used which may be typically selected e.g. from silanes or any other well known external donors in the field. External donors are known in the art and are used as stereoregulating agent in propylene polymerization. The external donors are preferably selected from diethylamino-triethoxy-silane (U-Donor), hydrocarbyloxy silane compounds and hydrocarbyloxy alkane compounds.
  • U-Donor diethylamino-triethoxy-silane
  • hydrocarbyloxy silane compounds hydrocarbyloxy alkane compounds.
  • Typical hydrocarbyloxy silane compounds have the formula (II) R' 0 Si(OR") 4-0 (II) wherein
  • the organo silane compounds are diethylamino-triethoxy-silane (U-Donor), cyclohexylmethyl dimethoxy silane (C-Donor), or dicyclopentyl dimethoxy silane (D-Donor), the latter especially preferred.
  • the solid catalyst system according to the emulsion method is obtained by
  • the complex (C) is preferably dissolved in an C 6 to C 10 aromatic hydrocarbon, like toluene and contacted with a liquid transition metal compound (CT), preferably with a liquid transition metal compound (CT) of transition metals of groups 4 to 6, in particular of group 4, of the periodic table (IUPAC), like Ti (e.g. TiC1 4 ).
  • CT liquid transition metal compound
  • IUPAC periodic table
  • Ti e.g. TiC1 4
  • the production of a two-phase, i.e. of an emulsion is encouraged by carrying out the contacting at low temperature, specifically above 10 °C but below 60 °C, preferably between above 20 °C and below 50 °C.
  • the emulsion comprises a continuous phase and a dispersed phase in form of droplets. In the dispersed phase the complex (C) as well as the transition metal compound (CT) are present
  • Additional catalyst components like an aluminium compound, like aluminium alkyl, aluminium alkyl halide or aluminium alkoxy or aluminium alkoxy alkyl or halide or other compounds acting as reducing agents can be added to the reactions mixture at any step before the final recovery of the solid catalyst system.
  • any agents enhancing the emulsion formation can be added.
  • emulsifying agents or emulsion stabilisers e.g. surfactants, like acrylic or metacrylic polymer solutions and turbulence minimizing agents, like alpha-olefin polymers without polar groups, like polymers of alpha olefins of 6 to 20 carbon atoms.
  • Suitable processes for mixing the obtained emulsion include the use of mechanical as well as the use of ultrasound for mixing, as known to the skilled person.
  • the process parameters such as time of mixing, intensity of mixing, type of mixing, power employed for mixing, such as mixer velocity or wavelength of ultrasound employed, viscosity of solvent phase, additives employed, such as surfactants, etc. are used for adjusting the size of the solid catalyst system (SCS) particles.
  • SCS solid catalyst system
  • Said solid catalyst system (SCS) particles may then be formed and recovered in usual manner, including the solidification of the catalyst particles by heating (for instance at a temperature of 70 to 150 °C, more preferably at 90 to 110 °C) and separating steps (for recovering the catalyst particles).
  • heating for instance at a temperature of 70 to 150 °C, more preferably at 90 to 110 °C
  • separating steps for recovering the catalyst particles.
  • the solid catalyst particles (SCS) obtained may furthermore be subjected to further post-processing steps, such as washing, stabilizing, pre-polymerization, prior to the final use in polymerisation process.
  • the solid catalyst system according to the precipitation method is obtained by
  • the complex (C) is preferably dissolved in an C 6 to C 10 aromatic hydrocarbon, like toluene and contacted with a liquid transition metal compound (CT), i.e. with a transition metal compound (CT) being not solid.
  • CT transition metal compound
  • the transition metal compound (CT) as such is a liquid or it is dissolved in a solvent at ambient temperatures, i.e. at temperatures up to 80 °C (20 to 80 °C).
  • a solvent is used for the transition metal compound (CT) it can be any organic solvent and can be the same as the organic solvent used for the complex (C) or can be different thereto, the latter being preferred.
  • the organic solvent for the transition metal compound (CT) is C 5 to C 10 hydrocarbon, more preferably of a C 6 to C 10 alkane, like heptanes, octane or nonane, or any mixtures thereof.
  • the transition metal compound (CT) is preferably a transition metal compound (CT) of transition metals of groups 4 to 6, in particular of group 4, of the periodic table (IUPAC), like Ti (e.g. TiCl 4 ). Due to the contact of the solution of the complex (C) with the liquid transition metal compound (CT) or with a solution of the transition metal compound (CT) precipitation occurs and the solid catalyst system (SCS) is formed.
  • precipitation means that during the catalyst preparation a chemical reaction in a solution takes place leading to the desired catalyst system insoluble in said solution.
  • Such a precipitated solid catalyst system is different in form and shape to a solid catalyst system obtained by the emulsion method discussed above.
  • the combining of the solution of the complex (C) with the liquid transition metal compound (CT) or with the solution of the transition metal compound (CT) is effected at a temperature of at least 50 °C, preferably in the temperature range of 50 to 110 °C, like in the temperature range of 70 to 100 °C, most preferably in the range of 85 to 95 °C. It is especially appreciated that after having combined the complex (C) and the transition metal compound (CT) that the whole reaction mixture is kept at least at 50 °C, more preferably is kept in the temperature range of 50 to 110 °C, like 70 to 100 °C, most preferably in the range of 85 to 95 °C, to secure full precipitation of the catalyst in form of a solid particle.
  • a precipitating agent according to this invention is an agent which promotes the precipitation of the catalyst system in form of a solid particle.
  • the organic solvent used for the transition metal compound (CT) can promote the precipitating and thus act and used as a precipitating agent.
  • the final catalyst does not contain such a medium.
  • the particle size of the seed materials might be undesirable big and might negatively influence the electrical properties. Accordingly it is appreciated that the solid catalyst system (SCS) used in the present application is free of any precipitating agent residues. "Free” in this context throughout the invention means that not more than 1.0 wt.-%, preferably not more than 0.5 wt.-%, more preferably not more than 0.05 wt.-%, still more preferably not more than 0.005 wt.-%, yet more preferably no detectable precipitating agent is present within the solid catalyst system (SCS).
  • Additional catalyst components like the cocatalyst and/or the external donor, as described above, can be used as normally in olefin polymerisation catalyst.
  • Suitable mixing techniques include the use of mechanical as well as the use of ultrasound for mixing, as known to the skilled person.
  • the solvent for the complex (C) on the one hand and the solvent of the transition metal compound (CT) on the other hand are selected in a way which supports the immediate precipitation of the solid catalyst system.
  • the solvent for the complex (C) comprises, preferably consists of, C 5 to C 10 hydrocarbon, more preferably of a C 6 to C 10 aromatic hydrocarbon, like toluene.
  • the solvent where the transition metal compound (CT), like TiCl 4 , can be solved, can be the same as for the complex (C) or can be different thereto, the latter being preferred.
  • the solvent for the transition metal compound (CT) is C 5 to C 10 hydrocarbon, more preferably of a C 6 to C 10 alkane, like heptanes, octane or nonane, or any mixtures thereof. It is in particular appreciated that the solvent for the complex (C) is C 6 to C 10 aromatic hydrocarbon, like toluene, and the solvent for the transition metal compound (CT) is a C 6 to C 10 alkane, like heptanes.
  • solid catalyst system (SCS) particle After precipitation the solid catalyst system (SCS) particle is washed in a known manner. Accordingly it is preferred that solid catalyst system (SCS) particle is washed with toluene, preferably with hot (e. g. 90 °C) toluene and subsequently with heptane, most preferably with hot (e. g. 90 C) heptane. Further washings, e.g. with gold heptanes, or pentane are possible as well.
  • toluene preferably with hot (e. g. 90 °C) toluene and subsequently with heptane, most preferably with hot (e. g. 90 C) heptane.
  • Further washings e.g. with gold heptanes, or pentane are possible as well.
  • EP 2 251 361 For further information with regard to the precipitation method reference is made to EP 2 251 361 .
  • the propylene copolymer (R-PP) has a the melt flow rate MFR 2 (230 °C) measured according to ISO 1133 in the range of equal or more than 65 g/10min to equal or below 200 g/10min, preferably in the range of equal or more than 70 g/10min to equal or below 150 g/10min, still more preferably in the range of 75.0 to 130.0 g/10min.
  • the propylene copolymer (R-PP) according to this invention is featured by its comonomer content.
  • a "comonomer” according to this invention is a polymerizable unit different to propylene.
  • the propylene copolymer (R-PP) according to this invention has a comonomer content in the range of equal or more than 1.5 to equal or below 8.0 wt.-%, still more preferably in the range of equal or more than 2.5 to equal or below 6.0 wt.-%, yet more preferably in the range of equal or more than 3.0 to equal or below 5.5 wt.-%.
  • the propylene copolymer (R-PP) comprises comonomers copolymerizable with propylene, for example comonomers such as ethylene and/or C 4 to C 12 ⁇ -olefins, in particular ethylene and/or C 4 to C 8 ⁇ -olefins, e.g. 1-butene and/or 1-hexene.
  • the propylene copolymer (R-PP) according to this invention comprises, especially consists of, monomers copolymerizable with propylene from the group consisting of ethylene, 1-butene and 1-hexene.
  • the propylene copolymer (R-PP) of this invention comprises - apart from propylene - units derivable from ethylene and/or 1-butene.
  • the propylene copolymer (R-PP) comprises units derivable from ethylene and propylene only.
  • propylene copolymer is a propylene copolymer of propylene and ethylene only, wherein the ethylene content is in the range of equal or more than 1.5 to equal or below 8.0 wt.-%, more preferably in the range of equal or more than 2.5 to equal or below 6.0 wt.-%, yet more preferably in the range of equal or more than 3.0 to equal or below 5.5 wt.-%.
  • the propylene copolymer (R-PP) as well as the propylene copolymer fraction (C-A) and the propylene copolymer fraction (B) according to this invention are preferably random propylene copolymers.
  • the term "random copolymer” has to be preferably understood according to IUPAC ( Pure Appl. Chem., Vol. No. 68, 8, pp. 1591 to 1595, 1996 ).
  • the molar concentration of comonomer dyads like ethylene dyads, obeys the relationship [HH] ⁇ [H] 2 wherein
  • the propylene copolymer (R-PP) as well as the polypropylene fraction (A) and the propylene copolymer fraction (B) as defined in detail below are isotactic. Accordingly it is appreciated that the propylene copolymer (R-PP), the polypropylene fraction (A) and the propylene copolymer fraction (B) have a rather high isotactic triad concentration, i.e. higher than 90 %, more preferably higher than 92 %, still more preferably higher than 93 % and yet more preferably higher than 95 %, like higher than 97 %.
  • the molecular weight distribution is the relation between the numbers of molecules in a polymer and the individual chain length.
  • the molecular weight distribution (MWD) is expressed as the ratio of weight average molecular weight (M w ) and number average molecular weight (M n ).
  • the number average molecular weight (M n ) is an average molecular weight of a polymer expressed as the first moment of a plot of the number of molecules in each molecular weight range against the molecular weight. In effect, this is the total molecular weight of all molecules divided by the number of molecules.
  • the weight average molecular weight (M w ) is the first moment of a plot of the weight of polymer in each molecular weight range against molecular weight.
  • the propylene copolymer (R-PP) has a weight average molecular weight (M w ) from 80 to 400 kg/mol, more preferably from 120 to 350 kg/mol.
  • propylene copolymer (R-PP) is featured by a moderately broad molecular weight distribution. Accordingly the propylene copolymer (R-PP) has a molecular weight distribution (MWD) in the range of 4.0 to equal or below 7.0, preferably in the range of 4.5 to 6.5.
  • MWD molecular weight distribution
  • the main melting temperature (T m ) as measured by DSC according to ISO 11357-3 of the propylene copolymer (R-PP) is preferably at least 138 °C, more preferably of at least 145 °C.
  • the melting temperature (T m ) measured according to ISO 11357-3 of the propylene copolymer (R-PP) is in the range of 138 to 158 °C, more preferably in the range of 140 to 155 °C.
  • the propylene copolymer (R-PP) can be defined by the xylene cold soluble (XCS) content measured according to ISO 16152 (25 °C). Accordingly the propylene copolymer (R-PP) is preferably featured by a xylene cold soluble (XCS) content of below 20.0 wt.-%, more preferably of equal or below 15.0 wt.-%, yet more preferably equal or below 12.0 wt.-%.
  • XCS xylene cold soluble
  • the propylene copolymer (R-PP) of the instant invention has a xylene cold soluble (XCS) content in the range of 3.0 to 20.0 wt.-%, more preferably in the range of 5.0 to 15.0 wt.-%, yet more preferably in the range of 6.5 to 13.0 wt.-%.
  • XCS xylene cold soluble
  • the amount of xylene cold soluble (XCS) additionally indicates that the propylene copolymer (R-PP) is preferably free of any elastomeric polymer component, like an ethylene propylene rubber.
  • the propylene copolymer (R-PP) shall be not a heterophasic polypropylene, i.e. a system consisting of a polypropylene matrix in which an elastomeric phase is dispersed. Such systems are featured by a rather high xylene cold soluble content.
  • the propylene copolymer (R-PP) comprises the polypropylene fraction (A) and the propylene copolymer fraction (B) as the only polymer components.
  • the propylene copolymer (R-PP) of the present invention is further defined by its polymer fractions present. Accordingly the propylene copolymer (R-PP) of the present invention comprises at least, preferably consists of, two fractions, namely the polypropylene fraction (A), which is produced in the first reactor (R-1) and the propylene copolymer fraction (B), which is produced in the second reactor (R-2).
  • weight ratio of the polypropylene fraction (A) to the propylene copolymer fraction (B) [(A)/(B)] is of 30/70 to 70/30, preferably of 35/65 to 65/35, more preferably of 45/55 to 55/45.
  • polypropylene fraction (A) is preferably the comonomer lean fraction whereas the propylene copolymer fraction (B) is the comonomer rich fraction.
  • the polypropylene (A) has a comonomer content of equal or below 4.0 wt.-%, more preferably of equal or below 3.0 wt.-%. Accordingly the polypropylene fraction (A) is a propylene copolymer fraction (C-A).
  • the comonomer content is in the range of equal or more than 0.5 to equal or below 3.0 wt.-%.
  • propylene copolymer fraction (C-A) is a random propylene copolymer.
  • the propylene copolymer fraction (C-A) comprises comonomers copolymerizable with propylene, for example comonomers such as ethylene and/or C 4 to C 12 ⁇ -olefins, in particular ethylene and/or C 4 to C 8 ⁇ -olefins, e.g. 1-butene and/or 1-hexene.
  • comonomers such as ethylene and/or C 4 to C 12 ⁇ -olefins, in particular ethylene and/or C 4 to C 8 ⁇ -olefins, e.g. 1-butene and/or 1-hexene.
  • the propylene copolymer fraction (C-A) according to this invention comprises, especially consists of, monomers copolymerizable with propylene from the group consisting of ethylene, 1-butene and 1-hexene.
  • propylene copolymer fraction (C-A) of this invention comprises - apart from propylene - units derivable from ethylene and/or 1-butene.
  • the propylene copolymer fraction (C-A) comprises units derivable from ethylene and propylene only.
  • the propylene copolymer fraction (C-A) is in one preferred embodiment a propylene copolymer of propylene and ethylene only, wherein the ethylene content is in the range of equal or more than 0.2 to equal or below 4.0 wt.-%, preferably in the range equal or more than 0.5 to equal or below 3.0 wt.-%.
  • the propylene copolymer fraction (B) preferably has a higher comonomer content than the polypropylene fraction (A). Accordingly the propylene copolymer fraction (B) has a comonomer content of equal or more than 2.5 wt.-% to equal or below 10.0 wt.-%, more preferably of equal or more than 3.0 to 10.0 wt.-%, still more preferably of equal or more than 3.5 to 10.0 wt.-%.
  • the propylene copolymer (B) is a random propylene copolymer.
  • the propylene copolymer fraction (B) comprises comonomers copolymerizable with propylene, for example comonomers such as ethylene and/or C 4 to C 12 ⁇ -olefins, in particular ethylene and/or C 4 to C 8 ⁇ -olefins, e.g. 1-butene and/or 1-hexene.
  • comonomers such as ethylene and/or C 4 to C 12 ⁇ -olefins, in particular ethylene and/or C 4 to C 8 ⁇ -olefins, e.g. 1-butene and/or 1-hexene.
  • the propylene copolymer fraction (B) according to this invention comprises, especially consists of, monomers copolymerizable with propylene from the group consisting of ethylene, 1-butene and 1-hexene.
  • the propylene copolymer fraction (B) of this invention comprises - apart from propylene - units derivable from ethylene and/or 1-butene.
  • the propylene copolymer fraction (B) comprises units derivable from ethylene and propylene only.
  • the propylene copolymer fraction (B) is in one preferred embodiment a propylene copolymer of propylene and ethylene only, wherein the ethylene content is of equal or more than 2.5 wt.-% to equal or below 16.0 wt.-%, more preferably of equal or more than 3.0 to 12.0 wt.-%, still more preferably of equal or more than 3.5 to 10.0 wt.-%.
  • the comonomers of the propylene copolymer fraction (C-A) and of the propylene copolymer fraction (B) are the same.
  • the propylene copolymer (R-PP) of the instant invention comprises, preferably comprises only, a propylene copolymer fraction (C-A) and a propylene copolymer fraction (B), in both polymers the comonomer is only ethylene.
  • polypropylene fraction (A) is preferably the comonomer lean fraction whereas the propylene copolymer fraction (B) is the comonomer rich fraction. Accordingly the comonomer content in the polypropylene fraction (A) is lower compared to the comonomer content of the propylene copolymer fraction (B).
  • the propylene copolymer (R-PP) fulfils the correlation com (R-PP) / com (A) being in the range of more than 0 to 10.0, like 1.1 to 10.0, more preferably being in the range of 1.2 to 6.0, still more preferably in the range of 1.5 to 5.0, wherein
  • the equation is in particular applicable in case the polypropylene fraction (A) is a propylene copolymer fraction (C-A) as defined above.
  • the polypropylene fraction (A) and the propylene copolymer fraction (B) of the propylene copolymer (R-PP) differ in the melt flow rate only to some extent, if at all. Accordingly the ratio MFR (A)/MFR (R-PP) is in the range of 0.70 to 1.20, more preferably 0.75 to 1.20, yet more preferably in the range of 0.80 to 1.00, wherein
  • the polypropylene fraction (A) has a melt flow rate MFR 2 (230 °C) measured according to ISO 1133 in the range of equal or more than 68 g/10min to equal or below 200 g/10min, preferably in the range of equal or more than 70 g/10min to equal or below 180 g/10min, still more preferably in the range of 72.0 to 150.0 g/10min.
  • the propylene copolymer fraction (B) has a melt flow rate MFR 2 (230 °C) measured according to ISO 1133 in the range of equal or more than 60 g/10min to equal or below 180 g/10min, preferably in the range of equal or more than 65 g/10min to equal or below 130 g/10min, still more preferably in the range of 70.0 to 120.0 g/10min.
  • polypropylene fraction (A) has preferably a xylene cold soluble (XCS) content of below 6.0 wt.-%, more preferably of below 5.5 wt.-%, i.e. below 5.0 wt.-%, still more preferably in the range of 2.0 to 6.0 wt.-%, yet more preferably in the range of 2.5 to 5.5 wt.-%, still yet more preferably in the range of 2.8 to 5.0 wt.-%.
  • XCS xylene cold soluble
  • the polypropylene fraction (A) has a lower xylene cold soluble (XCS) content than the propylene copolymer fraction (B). Accordingly it is preferred that the propylene copolymer fraction (B) has preferably a xylene cold soluble (XCS) content in the range of 3.0 to 20.0 wt.-%, yet more preferably in the range of 4.5 to 15.0 wt.-%.
  • XCS xylene cold soluble
  • the propylene copolymer (R-PP) obtained by the process of the instant invention comprises a propylene copolymer fraction (C-A) and a propylene copolymer fraction (B) in the weight ratio [(C-A)/(B)] of 30/70 to 70/30, wherein said propylene copolymer (R-PP) has
  • the propylene copolymer (R-PP) may contain additives known in the art, like antioxidants, nucleating agents, slip agents and antistatic agents. However the amount of additives shall not more 10 wt.-%, more preferably not more than5 wt.-%, still more preferably shall not more than 2 wt.-% within the propylene copolymer (R-PP).
  • the present invention is also directed to thin wall packaging elements, i.e. thin wall packaging elements having a thickness of equal or below 2 mm, preferably in the range of 0.2 to 2.0 mm.
  • the thin wall packaging elements according to this invention comprise at least 70 wt.-%, more preferably comprise at least 90 wt.-%, yet more preferably comprise at least 95 wt.-%, still more preferably consisting of, a propylene copolymer (R-PP) as defined herein.
  • Said thin wall packaging elements are preferably produced by injection molding
  • the thin wall packaging elements are preferably selected from the group consisting of cups, boxes, trays, pails, buckets, bowls, lids, flaps, caps, CD covers, DVD covers and the like.
  • Comonomer content is measured with Fourier transform infrared spectroscopy (FTIR) calibrated with 13 C-NMR.
  • FTIR Fourier transform infrared spectroscopy
  • a thin film of the sample was prepared by hot-pressing.
  • the area of absorption peaks 720 and 733 cm -1 for propylene-ethylene-copolymers was measured with Perkin Elmer FTIR 1600 spectrometer.
  • Propylene-1-butene-copolymers were evaluated at 767 cm -1 .
  • the method was calibrated by ethylene content data measured by 13 C-NMR. See also " IR-Spektroskopie für Anwender"; WILEY-VCH, 1997 and “ Validierung in der Analytik", WILEY-VCH, 1997
  • Mw/Mn/MWD are measured by Gel Permeation Chromatography (GPC) according to the following method:
  • melt flow rates are measured with a load of 2.16 kg (MFR 2 ) at 230 °C.
  • the melt flow rate is that quantity of polymer in grams which the test apparatus standardised to ISO 1133 extrudes within 10 minutes at a temperature of 230 °C under a load of 2.16 kg.
  • XCS xylene cold solubles
  • melt- and crystallization enthalpy were measured by the DSC method according to ISO 11357-3.
  • Charpy notched impact strength is determined according to ISO 179 / 1eA at 23 °C, and at 0 °C by using injection moulded test specimens as described in EN ISO 1873-2 (80 x 10 x 4 mm).
  • Haze was determined according to ASTM D1003 on injection molded plaques of 60x60 mm 2 area and a thickness of 1 resp. 2 mm produced as described in EN ISO 1873-2. Puncture energy is determined in the instrumental falling weight (IFW) test according to ISO 6603-2 using injection moulded plaques of 60x60x2 mm 3 . Puncture energy reported results from an integral ofthe failure energy curve measured at +23°C.
  • Porosity BET with N 2 gas, ASTM 4641, apparatus Micromeritics Tristar 3000; sample preparation: at a temperature of 50 °C, 6 hours in vacuum.
  • Mean particle size is given in nm and measured with Coulter Counter LS200 at room temperature with n-heptane as medium; particle sizes below 100 nm by transmission electron microscopy.
  • the catalyst A used in the polymerization processes ofthe inventive examples IE1 to IE4 was the catalyst of the example section of WO 2010009827 A1 (see pages 30 and 31)
  • the catalyst B used in the polymerization processes of comparative examples CE1 and CE2 was the commercial BCF20P catalyst (1.9 wt Ti-Ziegler-Natta-catalyst as described in EP 591 224 ) of Borealis with triethyl-aluminium (TEA) as co-catalyst and dicyclo pentyl dimethoxy silane as donor.
  • TAA triethyl-aluminium
  • the aluminium to donor ratio was 5 mol/mol.
  • the catalyst was prepolymerized with vinyl cyclohexane in an amount to achieve a concentration of 200 ppm poly(vinyl cyclohexane) (PVCH) in the final polymer.
  • PVCH poly(vinyl cyclohexane)
  • the propylene copolymers (R-PP) of table 1 have been produced in a Borstar PP pilot plant in a two-step polymerization process starting in prepolimerization reactor, followed by a bulk-phase loop reactor and subsequently by polymerization in a gas phase reactor, varying the molecular weight as well as ethylene content by appropriate hydrogen and comonomer feeds.
  • Comparative example 3 is the commercial random propylene copolymer RJ900MO from Borealis Polyolefine GmbH, Austria.
  • Table 1 Preparation of the propylene copolymers (R-PP) CE1 CE2 IE1 IE2 IE3 IE4 Catalyst [-] B A A A A A Donor [-] D D D D D D Prepol T [°C] 25 30 30 30 30 30 30 30 p [bar] 52 54 53 54 53 54 t RES [h] 0.35 0.35 0.34 0.34 0.35 0.34 C 2 [wt.-%] 0 0 0.4 0.4 0.5 0.5 Loop T [°C] 65 70 80 80 80 80 80 p [bar] 55 56 58 58 58 58 tRES [h] 0.38 0.38 0.29 0.27 0.39 0.25 MFR 2 [g/ 10 min] 302 100 108 105 76 103 C 2 [wt.-%] 0 1.5 1.4 1.4 1.3 1.5 XCS [wt.-%]

Claims (11)

  1. Propylen-Copolymer (R-PP), umfassend eine Propylen-Copolymer-Fraktion (C-A) und eine Propylen-Copolymer-Fraktion (B) in dem Gewichtsverhältnis [(C-A)/(B)] von 30/70 bis 70/30, wobei das Propylen-Copolymer (R-PP) aufweist
    (a) einen Comonomer-Gehalt in dem Bereich von gleich oder mehr als 1,5 bis gleich oder unter 8,0 Gew.-%, wobei die Comonomere Ethylen und/oder C4 bis C12 α-Olefine darstellen,
    und
    (b) eine Schmelze-Massefließ-Rate MFR2 (230 °C), gemessen gemäß ISO 1133, von gleich oder mehr als 65 bis gleich oder unter 200 g/10 min,
    und
    (c) eine Molekulargewichts-Verteilung (MWD), gemessen durch Gelpermeations-Chromatographie (GPC), in dem Bereich von gleich oder mehr als 4,0 bis gleich oder unter 7,0,
    wobei weiterhin
    (d) die Propylen-Copolymer-Fraktion (C-A) einen Comonomer-Gehalt in dem Bereich von gleich oder mehr als 0,5 bis gleich oder unter 3,0 Gew.-% aufweist, wobei die Comonomere Ethylen und/oder C4 bis C12 α-Olefine darstellen, und
    (e) die Propylen-Copolymer-Fraktion (B) einen Comonomer-Gehalt in dem Bereich von gleich oder mehr als 2,5 bis gleich oder unter 10,0 Gew.-% aufweist, wobei die Comonomere Ethylen und/oder C4 bis C12 α-Olefine darstellen.
  2. Propylen-Copolymer (R-PP) nach Anspruch 1, wobei die Propylen-Copolymer-Fraktion (C-A) die an Comonomer arme Fraktion darstellt und die Propylen-Copolymer-Fraktion (B) die an Comonomer reiche Fraktion darstellt.
  3. Propylen-Copolymer (R-PP) nach Anspruch 1 oder 2, wobei die Propylen-Copolymer-Fraktion (B) einen Comonomer-Gehalt in dem Bereich von gleich oder mehr als 3,5 bis gleich oder unter 10,0 Gew.-% aufweist.
  4. Propylen-Copolymer (R-PP) nach einem der vorangehenden Ansprüche, wobei das Verhältnis MFR (C-A) / MFR (R-PP) in dem Bereich von 0,70 bis 1,20 liegt,
    wobei
    MFR (C-A) die Schmelze-Massefließ-Rate MFR2 (230 °C) [g/10 min], gemessen gemäß ISO 1133, der Polypropylen-Copolymer-Fraktion (A) darstellt,
    MFR (R-PP) die Schmelze-Massefließ-Rate MFR2 (230 °C) [g/10 min], gemessen gemäß ISO 1133, des Propylen-Copolymers (R-PP) darstellt.
  5. Propylen-Copolymer (R-PP) nach einem der vorangehenden Ansprüche, wobei die Propylen-Copolymer-Fraktion (C-A) aufweist
    (a) eine Schmelze-Massefließ-Rate MFR2 (230°C), gemessen gemäß ISO 1133, in dem Bereich von 68 bis 200 g/10 min,
    und/oder
    (b) einen in Xylol löslichen Gehalt (XCS), bestimmt bei 25°C gemäß ISO 16152, von unter 5,0 Gew.-%.
  6. Propylen-Copolymer (R-PP) nach einem der vorangehenden Ansprüche, wobei die Propylen-Copolymer-Fraktion (B) aufweist
    (a) eine Schmelze-Massefließ-Rate MFR2 (230°C), gemessen gemäß ISO 1133, in dem Bereich von 60 bis 180 g/10 min,
    und/oder
    (b) einen in Xylol löslichen Gehalt (XCS), bestimmt bei 25°C gemäß ISO 16152, in dem Bereich von gleich oder mehr als 3,0 bis gleich oder unter 20,0 Gew.-%.
  7. Propylen-Copolymer (R-PP) nach einem der vorangehenden Ansprüche, wobei das Propylen-Copolymer (R-PP) aufweist
    (a) einen in Xylol löslichen Gehalt (XCS), bestimmt bei 25°C gemäß ISO 16152, in dem Bereich von gleich oder mehr als 3,0 bis gleich oder unter 20,0 Gew.-%, und/oder
    (b) eine Schmelztemperatur Tm, bestimmt durch dynamische Differenz-Kalorimetrie (DSC), von mindestens 138°C.
  8. Dünnwandige Verpackung, umfassend ein Propylen-Copolymer (R-PP) nach einem der vorangehenden Ansprüche.
  9. Dünnwandige Verpackung, umfassend ein Propylen-Copolymer (R-PP) nach Anspruch 8, wobei die dünnwandige Verpackung mindestens 70 Gew.-% des Propylen-Copolymers (R-PP) umfasst.
  10. Dünnwandige Verpackung, umfassend ein Propylen-Copolymer (R-PP) nach Anspruch 8 oder 9, wobei die Verpackung eine Dicke von gleich oder unter 2 mm aufweist.
  11. Dünnwandige Verpackung nach einem der vorangehenden Ansprüche 8 bis 11, wobei die Verpackung ausgewählt ist aus der Gruppe, bestehend aus Bechern, Kästen, Ablagen, Eimern, Kübeln, Schalen, Deckeln, Klappen, Verschlussteilen, CD-Hüllen und DVD-Hüllen.
EP11189574.4A 2011-05-23 2011-05-23 Zufälliges Propylencopolymer mit hoher Steifigkeit und geringer Trübung Active EP2527594B1 (de)

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PL11189574T PL2527594T3 (pl) 2011-05-23 2011-05-23 Bezładny kopolimer propylenu o dużej sztywności i małym zmętnieniu
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ES2266053T3 (es) 2001-06-20 2007-03-01 Borealis Technology Oy Preparacion de un componente de catalizador para la polimerizacion de olefina.
EP1607433B1 (de) * 2001-06-27 2016-08-10 Borealis Technology Oy Statistisches Propylencopolymer enthaltende Polymerfolie
EP1403292B1 (de) 2002-09-30 2016-04-13 Borealis Polymers Oy Verfahren zur herstellung eines olefinpolymerisationskatalysatorbestandteils mit verbesserter aktivität bei hoher temperatur
EP1833910B1 (de) * 2004-12-17 2009-08-26 ExxonMobil Chemical Patents Inc. Polymerblends und vliesstoffe daraus
EP1803743B1 (de) 2005-12-30 2016-08-10 Borealis Technology Oy Katalysatorpartikel
ES2536254T3 (es) * 2006-06-30 2015-05-21 Borealis Technology Oy Copolímero de polipropileno al azar con alto flujo del fundido
EP2147939A1 (de) * 2008-07-22 2010-01-27 Borealis AG Polypropylenzusammensetzung mit verbesserter Optik für Folie und Formanwendungen
EP2251361B1 (de) 2009-05-04 2013-10-02 Borealis AG Herstellung präzipitierter ZN-PP-Katalysatoren mit Innenporenstruktur unter Verwendung von Nanoteilchen
EP2281851B1 (de) 2009-07-01 2011-09-07 Borealis AG Polypropylenzusammensetzung mit hohem Durchfluss

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CN103534442B (zh) 2016-11-09
CN103534442A (zh) 2014-01-22
EP2527593B1 (de) 2013-07-10
WO2012159927A1 (en) 2012-11-29
PL2527594T3 (pl) 2014-07-31
PL2527593T3 (pl) 2014-01-31
EP2527594A1 (de) 2012-11-28
ES2426273T3 (es) 2013-10-22
EP2527593A1 (de) 2012-11-28
ES2462165T3 (es) 2014-05-22

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